US4369247A - Process of producing relief structures using polyamide ester resins - Google Patents
Process of producing relief structures using polyamide ester resins Download PDFInfo
- Publication number
- US4369247A US4369247A US06/334,163 US33416381A US4369247A US 4369247 A US4369247 A US 4369247A US 33416381 A US33416381 A US 33416381A US 4369247 A US4369247 A US 4369247A
- Authority
- US
- United States
- Prior art keywords
- weight
- resin
- composition
- trimethylol propane
- polyamide ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/145—Polyamides; Polyesteramides; Polyimides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
Definitions
- This invention relates to a method for forming relief structures on electrical devices such as semiconductors, capacitors or printed circuits by using a polymeric heat resistant photopolymerizable composition.
- Photopolymerizable polymeric compositions used to form relief structures on electrical devices are well known as shown in Sigusch et al. U.S. Pat. Nos. 3,953,877 issued Apr. 27, 1976, Kleeberg et al. 3,957,512 issued May 18, 1976 and Rubner et al. 4,040,831 issued Aug. 9, 1977 now Re. No. 30,186 reissued Jan. 8, 1980.
- These compositions have limited commercial use since the radiation exposure time required to photopolymerize these compositions is too long for a modern process. In an efficient contact printing process, exposure times of 1 minute and preferably of 30 seconds or less are needed.
- the improved method of this invention uses a composition that can be photopolymerized in a relatively short time period of exposure to radiation.
- An improved method for the formation of relief structures on electrical devices wherein the relief structure consists of a stable heat resistant polyimide material comprising the steps of applying a solvent soluble radiation sensitive polyamide ester resin composition to a substrate, drying the composition, exposing the composition to radiation through a pattern, dissolving the unradiated portions and converting the resulted relief structure to form a polyimide structure;
- the improvement used in this method is a radiation polymerizable composition of a polyamide ester resin containing photopolymerizable groups, solvent for the resin; radiation sensitive polymerizable polyfunctional acrylate compound and photopolymerization initiator of aromatic biimidazole.
- a radiation polymerizable composition is used in the process to form relief structures on electrical devices such as capacitors and semiconductors.
- a solution of the composition is applied to a substrate such as a silicon wafer coated with a silicon dioxide layer and dried and forms a film on the substrate.
- the film is then exposed to radiation through a pattern and photopolymerized to form a relief structure.
- the unexposed and unpolymerized part of the film is dissolved off with a developer solution.
- the resulting relief structure is baked to remove the material not stable to heat and to form a polyimide structure with a sharp definition and with good mechanical, chemical and electrical properties.
- composition of a polyamide ester resin containing photopolymerizable groups the following constituents are used in the composition:
- Typical useful radiation sensitive polymerizable polyfunctional acrylate compounds are as follows: trimethylol propane trimethacrylate, trimethylol propane triacrylate, trimethylol propane ethoxylate trimethacrylate, trimethylol propane ethoxylate triacrylate, trimethylol propane polyethoxylate trimethacrylate, trimethylol propane polyethoxylate triacrylate and mixtures thereof.
- trimethylol propane polyethoxylate triacrylate having a weight average molecular weight of molecular weight of about 500-1500 and trimethylol propane ethoxylate triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, polymethylene diacrylate, polymethylene dimethacrylate, trimethylene glycol dimethacrylate.
- Typical aromatic biimadazole photo-polymerization initiators are disclosed by Chambers U.S. Pat. No. 3,479,185 issued Nov. 18, 1969 and Cescon U.S. Pat. No. 3,784,557 issued Jan. 8, 1974 which are hereby incorporated by reference.
- a 2,4,5-triphenyl imidazolyl dimer having an ortho substituent on the 2 phenyl ring is a particularly useful initiator.
- Typical initiators of this type are 2-o-chlorophenyl-4,5 diphenyl imidazolyl dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazolyl dimer, 2-(o-methyoxyphenyl) 4,5-diphenyl-imidazolyl dimer.
- hexaaryl biimidazoles can be used as photopolymerization initiators as shown in Fishman U.S. Pat. No. 3,552,973 issued Jan. 5, 1971.
- hydrogen donors, photoinitiators, photosensitizers or mixtures thereof in amounts of about 0.1-10% by weight, based on the weight of the resin, can be used in the composition.
- useful compounds include aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, 4-acryloxy-4'-diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, 2-t-butylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2,3-dichloronaphthoquinone, benzil dimethyl ketal, and other aromatic ketones such as disclosed in aforementioned U.S.
- benzoin benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, and benzoin phenyl ether, methylbenzoin, ethylbenzoin and other benzoins.
- Leuco dyes can be used such as those disclosed in aforementioned U.S. Pat. No. 3,552,973 col. 6, line 6 to col. 11, line 9 which disclosure is hereby incorporated by reference.
- useful dyes are alkyl amino-aromatic alkanes such as tris(diethylamino-o-tolyl) methane, tris(dimethylamino-o-oxylyl) methane and tris(dipropyl amino-o-tolyl) methane.
- the photopolymerizable resin used in the composition can be any type of resin that contains olefinic unsaturated groups that are photopolymerizable and that will form a polymer with good thermal, electrical and chemical properties.
- Polyamide ester resins are particularly useful. These resins are prepared according to the aforementioned Rubner U.S. Reissue Pat. No. 30,186 wherein an aromatic polycarboxylic acid anhydride is esterfied with a hydroxy alkyl acrylate or methacrylate which is then reacted with diamine. Typical aromatic polycarboxylic acid anhydrides and diamines are disclosed in Edwards U.S. Pat. No. 3,179,614 issued April 20, 1965 which disclosure is hereby incorporated by reference.
- Typical hydroxy alkyl acrylates and methacrylates are as follows: hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate, hydroxy ethyl methacrylate, hydroxpropyl methacrylate, hydroxybutyl methacrylate and the like.
- Typical useful polyamide ester resins have the following structure: ##STR1## where the ⁇ denotes isomerism, R is an aromatic radical, R 1 is an organic radical containing a photo polymerizable olefinic double bond, R 2 is an aromatic, aliphatic or cycloaliphatic radical and n is a positive integer sufficiently large to provide the resin with a weight average molecular weight of about 5,000 to 75,000.
- One particularly useful polyamide ester resin is the reaction product of pyromellitic dianhydride, hydroxy ethyl methacrylate and oxydianiline having a weight average molecular weight of about 15,000-60,000.
- Typical solvents that can be used alone or in combination to dissolve the polymer and to dilute the composition to an application viscosity are N-methylpyrrolidone, butyrolactone, ethylene glycol monoethyl ether, dimethyl formamide, dimethyl acetamide and hexamethylphosphoric acid triamide.
- the composition contains about 10-50 percent by weight, based on the weight of the composition, of polyamide ester resin containing photopolymerizable groups and about 50-90 percent by weight, based on the weight of the composition, of a solvent for the resin.
- Blends of these solvents with a nonsolvent can be used as a developer solution to remove resin that was not exposed to radiation and not polymerized.
- Typical developer solutions are 4-butyrolactone/toluene in a weight ratio from 20/1 or less to 1/4, dimethyl formamide/ethanol in a weight ratio from 20/1 to 1/4.
- Plasticizers can also be added to the composition in amounts of 0.1-10% by weight, based on the weight of the resin.
- Typical plasticizers are tricresyl phosphate, dioctyl phthalate, dihexyl phthalate, dinonyl phthalate, polyethylene glycol ethers, ethylene glycol dicaprolate.
- the composition is applied and then dried to form a film at about 30° to 100° C. for about 20 minutes to 5 hours.
- the film is then exposed through a pattern for about 1 second to 5 minutes.
- exposure times of 1-60 seconds are required and usually an exposure time under 30 seconds is much preferred.
- Typical radiation sources used are ultraviolet lamps providing a wave length of 250 to 400 nanometers and an intensity of 0.5-60 milliwatts per square centimeter (mW/cm 2 ).
- the film is then dipped or sprayed, with a developer solution and washed with a nonsolvent and then dried.
- the film is converted to a polyimide relief structure by baking at about 200°-400° C. for about 20 minutes to 4 hours. During conversion all the acrylate components are decomposed leaving a polyimide structure which is formed.
- the resulting relief structure has a sharp definition, good chemical, electrical and mechanical properties.
- compositions are as follows: protective coatings for semi-conductors, dielectric layers for multilayer integrated circuits, high temperature solder mask, bonding multilayer circuits, a final passivating coating on electrical devices, a photoresist and the like.
- the above constituents are changed into a container and the container is placed on a roller and mixed for about 2 hours and then the resulting composition is filtered through a 1 micron filter.
- a 2 inch diameter silicon wafer having a silicon dioxide coated is held at 300° C. for 10 minutes, cooled to room temperature and then is coated with an aminosilane adhesion promotor solution by a spin coating technique wherein the wafer is rotated at 3000 rpm for 30 seconds after the adhesion promotor solution is applied.
- the above prepared Composition A is reduced as follows: 10 parts Composition A to 1 part thinner (ethylene glycol monoethyl ether/n-methyl pyrrolidone -- 1/1 weight ratio) and the reduced composition is applied by the above spin technique using 3000 rpm for 10 seconds. The composition is exposed to an infrared (IR) light during the spin application. The coating of Composition A is then dried for 2 hours at 55° C.
- IR infrared
- the coated wafer is placed in a contact printer having a 500 Watt ultraviolet light source of 356 nanometers (nm) and an intensity of about 25 nW/cm 2 using a mask with lines spaced 4 microns apart and exposed for 5 seconds.
- the wafer is then developed by dipping the wafer for 10 seconds in a 1/1 solution of 4-butyrolactone/toluene and then rinsed for 5 seconds with a spray of toluene to remove any unexposed composition.
- the wafer then is cured at 300° C. for 1 hour to provide a relief structure about 4,500 Angstroms thick.
- Additional silicon wafers are prepared using the above procedure except the following exposure times are used 15 seconds, 20 seconds, 30 seconds, 45 seconds and 60 seconds. Exposure times of 15, 20 and 30 seconds result in clearly defined images which are acceptable but longer exposure times of 45 and 60 seconds result in poorer images due to over exposure.
- Additional silicon wafers are prepared using the above identical procedure except the following developer compositions are used: 4-butyrolactone/toluene in the following weight ratio 1/1.2, 1/1.4 and 1/1.6. All developers were adequate and gave an acceptable product.
- composition B which is representative of known compositions is prepared as follows:
- the constituents are mixed together using the same procedure as above and a silicon wafer is coated with the above adhesion promotor and with Composition B using the above coating and drying procedures.
- the coated wafer then is exposed as above (15, 20, 30, 45 and 60 seconds) to the aforementioned light source and developed using 4-butyrolactone/toluene ratio 1/1 developer solution.
- the coating is then cured as above. An underexposed unacceptable relief structure is formed. Exposure time to the light source had to be increased to 3.5 minutes before an acceptable image was formed.
- compositions are prepared by mixing the constituents as in Example 1:
- compositions are each coated onto a silicon wafer primed as in Example 1 with an adhesion promoter using the coating and baking procedure of Example 1.
- Each of the coatings then is exposed through a mask described in Example 1 for 1 minute using a 200 Watt light source having a surface intensity of 5.0 mW/cm 2 in the contact printer.
- Each of the coated wafers is developed in a 4-butyrolactone/toluene ratio of 1/3 developer solution for 20 seconds and rinsed for 10 seconds with toluene and cured as in Example 1. All wafers have acceptable images.
- the wafer made with Composition D has the best and most clear image.
- the wafer made with Composition C has the next best image which is better than the wafers made with Compositions E and F.
- the image on the wafer made with Composition F is slightly better than the image on the wafer made with Composition E.
- Composition B of Example 1 is coated onto a silicon wafer primed as in Example 1 using the above procedure.
- a 1 minute exposure time gave an underexposed unacceptable image.
- Exposure times had to be increased to about 5-7 minutes to provide a clear and distinct image on the wafer.
Abstract
Description
EXAMPLE 1 ______________________________________ Composition A Grams ______________________________________ Polyamide ester resin 10.00 (polymer of pyromellitic dianhydride and esterified with hydroxy ethyl methacrylate and reacted with 4,4'-oxydianiline and having a weight average molecular weight of about 25,000 prepared according to Example 2 of above U.S. Reissue Pat. No. 30,186) Bis (2-o-chlorophenyl-4,5-diphenylimidazolyl) 0.70 Michler's ketone (tetramethyl 0.25 diaminobenzophenone) Tris (diethylamino-o-tolyl)methane 0.25 Trimethylol propane polyethoxylate 2.0 triacrylate having a weight average molecular weight of about 1200 N--methylpyrrolidone 30.00 Total 43.20 ______________________________________
______________________________________ Grams ______________________________________ Polyamide ester resin 128.6 (described above) N--phenyl maleimide 6.4 Michler's ketone 2.60 N--methyl pyrrolidone 300.00 Total 437.6 ______________________________________
______________________________________ Composition C D E F ______________________________________ (grams) Polyamide ester resin 10.0 10.0 10.0 10.0 (described in Example 1) Bis (2-o-chlorophenyl-4,5- 0.7 0.7 -- -- diphenyl imidazolyl) Michler's ketone 0.25 0.25 0.2 0.2 Benzophenone -- -- 0.8 0.8 Tris (diethylamino-o- 0.20 0.20 -- -- tolyl)methane Trimethylol propane 2.0 -- 2.0 -- trimethacrylate Trimethlol propane -- 2.0 -- 2.0 triacrylate N--methyl pyrrolidone 30 30 30 30 Thinner (ethylene glycol 10 10 10 10 monoethyl ether/n-methyl pyrrolidone 1/1 ratio) ______________________________________
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/334,163 US4369247A (en) | 1980-09-03 | 1981-12-24 | Process of producing relief structures using polyamide ester resins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/183,648 US4329419A (en) | 1980-09-03 | 1980-09-03 | Polymeric heat resistant photopolymerizable composition for semiconductors and capacitors |
US06/334,163 US4369247A (en) | 1980-09-03 | 1981-12-24 | Process of producing relief structures using polyamide ester resins |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/183,648 Continuation-In-Part US4329419A (en) | 1980-09-03 | 1980-09-03 | Polymeric heat resistant photopolymerizable composition for semiconductors and capacitors |
Publications (1)
Publication Number | Publication Date |
---|---|
US4369247A true US4369247A (en) | 1983-01-18 |
Family
ID=26879387
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/334,163 Expired - Lifetime US4369247A (en) | 1980-09-03 | 1981-12-24 | Process of producing relief structures using polyamide ester resins |
Country Status (1)
Country | Link |
---|---|
US (1) | US4369247A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4701300A (en) * | 1985-01-15 | 1987-10-20 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Polyamide ester photoresist formulations of enhanced sensitivity |
US4828967A (en) * | 1984-12-26 | 1989-05-09 | Semiconductor Energy Laboratory Co., Ltd. | Electronic device and its manufacturing method |
US4873175A (en) * | 1986-01-08 | 1989-10-10 | Shinto Paint Co., Ltd. | Method of forming functional coating film between fine electric conductive circuits |
US5198325A (en) * | 1987-05-27 | 1993-03-30 | Hoechst Aktiengesellschaft | Photopolymerizable mixture, copying material containing same and process for producing highly heat-resistant relief structures wherein a trihalomethyl is the photoinitiator |
US5242551A (en) * | 1991-03-28 | 1993-09-07 | International Business Machines Corporation | Electron induced transformation of an isoimide to an n-imide and uses thereof |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3380831A (en) * | 1964-05-26 | 1968-04-30 | Du Pont | Photopolymerizable compositions and elements |
US3479185A (en) * | 1965-06-03 | 1969-11-18 | Du Pont | Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers |
US3552973A (en) * | 1967-07-20 | 1971-01-05 | Du Pont | Light sensitive hexaarylbiimidazole/p- aminophenyl ketone compositions |
US3623870A (en) * | 1969-07-22 | 1971-11-30 | Bell Telephone Labor Inc | Technique for the preparation of thermally stable photoresist |
US3784557A (en) * | 1962-03-21 | 1974-01-08 | Du Pont | Phototropic 2,4,5-triphenylimidazolyl radicals and dimers thereof |
US3953877A (en) * | 1973-05-23 | 1976-04-27 | Siemens Aktiengesellschaft | Semiconductors covered by a polymeric heat resistant relief structure |
US3957512A (en) * | 1973-02-22 | 1976-05-18 | Siemens Aktiengesellschaft | Method for the preparation of relief structures |
US4040831A (en) * | 1974-08-02 | 1977-08-09 | Siemens Aktiengesellschaft | Method for the preparation of relief structures |
US4093461A (en) * | 1975-07-18 | 1978-06-06 | Gaf Corporation | Positive working thermally stable photoresist composition, article and method of using |
US4117196A (en) * | 1976-12-23 | 1978-09-26 | W. R. Grace & Co. | Photocurable imidizable polyene-polythiol compositions |
US4132812A (en) * | 1977-09-02 | 1979-01-02 | W. R. Grace & Co. | Photocurable imidizable polyene-polythiol compositions |
US4188224A (en) * | 1976-02-23 | 1980-02-12 | Ciba-Geigy Corporation | Photopolymerizable composition containing anthrones |
-
1981
- 1981-12-24 US US06/334,163 patent/US4369247A/en not_active Expired - Lifetime
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3784557A (en) * | 1962-03-21 | 1974-01-08 | Du Pont | Phototropic 2,4,5-triphenylimidazolyl radicals and dimers thereof |
US3594410A (en) * | 1964-05-26 | 1971-07-20 | Du Pont | Addition polymerizable branched chain polyol polyesters of alpha-methylene carboxylic acids |
US3380831A (en) * | 1964-05-26 | 1968-04-30 | Du Pont | Photopolymerizable compositions and elements |
US3479185A (en) * | 1965-06-03 | 1969-11-18 | Du Pont | Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers |
US3552973A (en) * | 1967-07-20 | 1971-01-05 | Du Pont | Light sensitive hexaarylbiimidazole/p- aminophenyl ketone compositions |
US3623870A (en) * | 1969-07-22 | 1971-11-30 | Bell Telephone Labor Inc | Technique for the preparation of thermally stable photoresist |
US3957512A (en) * | 1973-02-22 | 1976-05-18 | Siemens Aktiengesellschaft | Method for the preparation of relief structures |
US3953877A (en) * | 1973-05-23 | 1976-04-27 | Siemens Aktiengesellschaft | Semiconductors covered by a polymeric heat resistant relief structure |
US4040831A (en) * | 1974-08-02 | 1977-08-09 | Siemens Aktiengesellschaft | Method for the preparation of relief structures |
US4093461A (en) * | 1975-07-18 | 1978-06-06 | Gaf Corporation | Positive working thermally stable photoresist composition, article and method of using |
US4188224A (en) * | 1976-02-23 | 1980-02-12 | Ciba-Geigy Corporation | Photopolymerizable composition containing anthrones |
US4117196A (en) * | 1976-12-23 | 1978-09-26 | W. R. Grace & Co. | Photocurable imidizable polyene-polythiol compositions |
US4132812A (en) * | 1977-09-02 | 1979-01-02 | W. R. Grace & Co. | Photocurable imidizable polyene-polythiol compositions |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4828967A (en) * | 1984-12-26 | 1989-05-09 | Semiconductor Energy Laboratory Co., Ltd. | Electronic device and its manufacturing method |
US4701300A (en) * | 1985-01-15 | 1987-10-20 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Polyamide ester photoresist formulations of enhanced sensitivity |
JPH0623840B2 (en) | 1985-01-15 | 1994-03-30 | チバ―ガイギー アクチエンゲゼルシヤフト | Highly sensitive polyamide ester photoresist composition |
US4873175A (en) * | 1986-01-08 | 1989-10-10 | Shinto Paint Co., Ltd. | Method of forming functional coating film between fine electric conductive circuits |
US5198325A (en) * | 1987-05-27 | 1993-03-30 | Hoechst Aktiengesellschaft | Photopolymerizable mixture, copying material containing same and process for producing highly heat-resistant relief structures wherein a trihalomethyl is the photoinitiator |
US5242551A (en) * | 1991-03-28 | 1993-09-07 | International Business Machines Corporation | Electron induced transformation of an isoimide to an n-imide and uses thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4329419A (en) | Polymeric heat resistant photopolymerizable composition for semiconductors and capacitors | |
US4414312A (en) | Photopolymerizable polyamide ester resin compositions containing an oxygen scavenger | |
US4416973A (en) | Radiation-sensitive polyimide precursor composition derived from a diaryl fluoro compound | |
US4454220A (en) | Electrical device containing a radiation-sensitive polyimide precursor composition derived from a diaryl fluoro compound | |
US4430418A (en) | Radiation-sensitive polyimide precursor composition derived from a diaryl fluoronated diamine compound | |
US4410612A (en) | Electrical device formed from polymeric heat resistant photopolymerizable composition | |
CA2025681A1 (en) | Photoreactive resin compositions developable in a semi-aqueous solution | |
US4369247A (en) | Process of producing relief structures using polyamide ester resins | |
JPH04288365A (en) | Photopolymer material | |
US4701300A (en) | Polyamide ester photoresist formulations of enhanced sensitivity | |
EP0084269B1 (en) | Radiation-sensitive polyimide precursor composition derived from a diaryl fluoro compound | |
Goff et al. | Radiation polymerizable compositions | |
JP2986970B2 (en) | Photosensitive resin composition | |
JPH0477741A (en) | Photosensitive resin composition | |
JPH0470661A (en) | Photosensitive resin composition | |
JPS58120636A (en) | Radiation-sensitive polyimide precursor composition | |
JP3064899B2 (en) | Composition, photosensitive composition using the same, photosensitive material, method for producing relief pattern, and method for producing polyimide pattern | |
JPH09325479A (en) | Manufacture of photosensitive composition, photosensitive material, relief pattern, and polyimide pattern | |
JPH0495962A (en) | Photosensitive resin composition | |
JPH03233457A (en) | Photosensitive resin composition | |
CN116794930A (en) | Negative polyimide photoresist, method for preparing concave-convex pattern and semiconductor device | |
JPH06102674A (en) | Pattern processing method for photosensitive polyamide acid ester resin composition | |
JP2002328471A (en) | Photosensitive composition, photosensitive material, method for producing relief pattern and method for producing polyimide pattern | |
JPH10228108A (en) | Photosensitive composition, photosensitive material, production of relief pattern and production of polyimide pattern | |
JPH11133598A (en) | Photosensitive composition, photosensitive material, production of relief pattern and production of polyimide pattern |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: E.I. DU PONT DE NEMOURS AND A COMPANY, WILMINGTON, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GOFF, DAVID L.;YUAN, EDWARD L.;PROSKOW, STEPHEN;REEL/FRAME:003967/0638 Effective date: 19811216 |
|
AS | Assignment |
Owner name: E.I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, D Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GOFF, DAVID L.;YUAN, EDWARD L.;PROSKOW, STEPHEN;REEL/FRAME:003980/0253 Effective date: 19811216 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M171); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M185); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 12 |